Skin cleaning composition



United States Patent 3,262,884 SIGN CLEANING CUMPQSITION .iames B. Myers, (Ianton, @hio, assignor to (Ihernical Supplies, Inc, Canton, Ghio, a corporation of Ohio In Drawing. Filed Jan. 16, 1963, Ser. No. 251,716

Claims. (Cl. 252-106) This invention relates to an oleaginous skin cleaner and more specifically to an oil base fluid containing an effective amount of permanganate. Still more specifically, this invention relates to an oleaginous base, and preferably an animal or vegetable oil containing an alkali metal permanganate .and a sequestering agent in amounts sufficient to provide an effective antiseptic skin cleaner. The oleaginous cleaner may contain, in addition to the permanganate and sequesterant, a substantial amount of water with a minor amount of detergent. The disinfectant or cleaning composition of this invention is a clear solution of permanganate in the oleaginous base, sequestered or solubilized with a small but effective amount of an alkali metal salt of a polyamino carboxylic acid.

The beneficial effect of soap and water on the skin has been recognized, particularly in medicine where it is used as a means of sterilizing. The precise nature of this sterilization, however, is not completely understood but it is believed that the soap helps to reduce the amount of bacteria on the skin simply by removing the microorganisms in the same manner as it removes other insoluble materials. There is some evidence, however, that soap as presently known is not limited to removing bacteria in this manner and some soaps have been found to be germicides for certain types of bacteria, meaning that for some forms of bacteria, such as the typhoid bacilli, it is inadequate and, therefore, other types of disinfectants are necessary. Thus, regardless of the kind of soap used, and the frequency and thoroughness with which scrubbing is performed, bacteria cannot be eliminated completely by the use of soap alone.

Cleanliness, without a doubt, is important to the proper functioning of the skin and while soap has been accepted generally as a cleaner, it has been shown that it will not remove some types of bacteria, which may be considered a form of invisible dirt. The oil solution of this invention is effective for this purpose and can be used in combination with soaps or in place thereof to remove great numbers of micro-organisms found on the skin surface, in the folds and fissures of the skin, and from beneath and around the nail edges in a direct and sanitary manner. The oleaginous skin cleaner will remove bacteria from the skin surface more efficiently than the common soaps in that it is capable of killing or altering the metabolism of different species of bacteria. Oil cleaners are particularly advantageous where Water is to be avoided and Where there is no objection to an oily feeling, which, if left on the skin, acts as a mild emollient or skin softener.

It has been recognized, particularly in the industrial cleaners, that improper cleaning contributes to the formation and extension of occupational dermatitis. This condition may become worse or continue long after the original cause has been removed if the cleaning agent is not effective in killing bacteria, particularly in industrial jobs, such as machinists. Here workers are continuously in contact with oily mixtures which, if not completely removed, eventually will have a harmful effect on the skin. These and similar occupational skin diseases can be avoided by the use of the present cleaner which removes the oily condition without harming the natural skin fats. The use of organic solvents for this purpose is irritating "ice and severely dries the skin. Thus, it is possible by using the antiseptic cleaner of this invention to reduce the incidence of oil dermatitis among those workers whose skin is very oily due to their occupation.

In cases where detergency is of primary importance, various synthetic detergents can be used in connection with the oleaginous cleaner. The detergent may be any of the known organic compounds which may contain, in addition, surface active properties which will enhance the cleaning and antiseptic properties of the composition. These detergents may be anionic, cationic, or nonionic, such -as the sulfated oils and alcohols, fatty esters, quaternary ammonium compounds, fat-ty amine salts, or polyether alcohols. A combination of the alkali metal permanganate with the oleaginous base, e.g. cocoanut oil, and the polyamino acid salts is effective with or without the detergents not only as a cleaner but as a disinfectant for open cuts and wounds for killing bacteria without having any deleterious effect.

Accordingly, it is an object of this invention to provide an oleaginous skin cleaner containing an effective amount of a disinfectant and, more specifically, to provide a vegetable or animal oil containing effective amounts of a disinfectant to be used as a skin cleaner and as an antiseptic for open wounds or cuts.

It is another object of this invention to provide a vegetable oil containing small amounts of an alkali metal permanganate as the disinfectant.

It is still another object of this invention to provide an oleaginous base containing small amounts of disinfectants and detergent capable of preventing industrial dermatitis and related skin disorders.

It is still another object of this invention to provide a clear and stable oleaginous fluid containing a substantial amount of water and small but effective amounts of disinfectants and detergents to be used in lieu of soap for cleaning and in preventing Ibacteria growth; more particularly, the use of the skin cleaner in industrial occupations where conventional soaps are not satisfactory.

It is still another object of this invention to provide a method of preparing a clear, oleaginous fluid having detergent and disinfecting properties sufficient to kill and prevent the growth of bacteria on the skin or in open cuts and wounds.

It is still another object of this invention to provide an antiseptic skin cleaner and a method of preparing same by utilizing a strong oxidizing agent in combination with vegetable oil and sequesterant to obtain a clear fluid capable of killing and preventing the growth of bacteria.

It is still another object of this invention to provide a method of solubilizing or sequestering large amounts of water in an oleaginous base together with minor amounts of a strong oxidizing agent and a detergent to be used as a disinfecting skin cleaner.

It is still another object of this invention to provide a vegetable or animal oil containing substantial amounts of water and an effective amount of a permanganate disinfectant.

These and other objects of the invention will become apparent from the further and more detailed description to follow:

It has been discovered, quite unexpectedly, that a strong oxidizing agent, such as potassium permanganate, can be dispersed or sequestered in an oleaginous base with metal salts of polyamino acids. More specifically, it has been discovered that the metal permanganates have unique germicidal effects on the skin or in open cuts and wounds when used as a solution in oil. These solutions are obtained by sequestering or solubilizing the permanganate in a mineral, animal, or vegetable oil. In addition, large amounts of water together with minor amounts of detergent can be dispersed or sequestered in the oil with the permanganate by using small amounts of met-a1 salts of polyamlno acids, suchas the sodium salt of ethylene diamine tetra-acetic acid.

The disinfectant or permanganate is an alkali metal permanganate, such as sodium and potassium permanganate, or mixtures thereof. The permanganate is dispersed in the oil in amounts ranging from about 0.001 to 3.0 percent by weight, with the sequesterant or the alkali metal salt of the polyamino polycarboxylic acid ranging from about 0.01 to 5.0 percent by weight of the total composition. In addition, up to 65 percent by weight of water, and up to 2.0 percent by weight of a detergent may be used in combination with the permanganate in the oleaginous base.

The detergents are used primarily as a cleaning agent for heavy industrial cleaners where foaming or soap characteristics are desired. The detergents include the sulfonated oils and fats of either animal or vegetable origin, the sulfonated fatty alcohols, or sulfated fatty ester amides, such as sulfated lauric acid amide. In addition, the sulfonated alkylated aromatic compounds, such as sulfonated lauryl benzene, sulfonated lauryl phenylether, sulfonated dioctyl succinate, or the phosphated fatty alcohols. Others include the hydroxylated fatty esters and ethers, such as the diethylene glycol stearates and polyether alcohols. Aside from these, other cationic materials, including the quaternary ammonium compounds or the fatty amine salts, which in themselves have some germicidal characteristics, may be used to enhance the soap and germicidal properties of the composition. These detergents may be used particularly in instances where natural or conventional soaps are irritating to individuals having skin diseases, such as eczema. However, even though these detergents are advisable in some instances, they are not essential and can be eliminated, depending upon the ultimate use of the cleaner. Thus, for example, where a disinfectant is of primary importance, the presence of the permanganate in the oleaginous base with the salt of the polyamino acid is sufficient to inhibit the growth and kill bacteria, and can be used on the skin prior to or after the use of conventional soaps.

The oleaginous base includes animal, vegetable, and mineral oils and, preferably, for purposes of this invention, the vegetable oils. These oils are essentially fatty acid esters containing small amounts of a free acid and some inorganic metal impurities, the amount depending upon the origin and the method employed in refining or purifying the oil. The presence of these metals, together with the metal permanganates, ordinarily would cause the metals to oxidize, if it were not for the addition of the amino acid which sequesters the metals and thus acts as an oxidation inhibitor. The metals catalyze oxidation of the oils to the extent that they become rancid and give off a strong odor, which makes them unsuitable for medicinal purposes. The presence, however, of the salt of the polyamino acids inhibits oxidation and provides a stable mixture which permits the permanganate to act as a germicide Without deleteriously affecting the oil. Most of these oils, and particularly vegetable oils, such as olive oil, linseed oil, castor oil, cotton seed oil, pine oil, and cocoanut oil, have saponification values ranging from about 180 to 200, or more, and in some instances may range up to 250. This indicates that the oils are essentially esters which can be saponified with strong bases, such as sodium or potassium hydroxide. For this reason, it may be advisable to add the sequesterant or polyamino salts to the oil before the addition of the permanganate, which, preferably, is added as an aqueous solution. These sequesterants may be the di-, tri-, or tetra-alkali metal salts of the pentaor tetra-polyamino acetic acids, or any mixtures thereof.

Typical examples which illustrate the skin cleaning composition of this invention are:

Example I Percent by weight Vegetable oil 30-99 Water 0-65 Alkali metal salt of alkylene polyamine polyacetic acid 0.01-5.0 Alkali metal permanganate 0.00l-2.0 Detergent 0-2.0 Coloring Perfume Example 11 Cocoanut oil 49-99 Water 10-50 Sodium salt of diethylene triamine pentaacetic acid 0.1-3.0 Potassium permanganate 0.00l-2.0 Sodium lauryl sulfate 0-2.0

Example Ill Cocoanut oil 60-90 Water 10-50 Tetrasodium salt of ethylene diamine tetraacetic acid 0.01-3.0 Potassium permanganate 0.01-2.0 Methyl parahydroxy benzoate 0-0.1 Oil of sassafras Example IV Palm oil 49-99 Water 0-50 Disodium salt of ethylene diamine tetra-acetic acid 0.01-5.0 Potassium permanganate 0.001-2.0 Sodium lauryl sulfate 0-2.0 Perfume Coloring Example V Olive oil 49-99 Water 0-65 Potassium salt of ethylene diamine tetra-acetic acid 0.01-5.0 Potassium permanganate 0.001-2.0 Detergent 02.0 Coloring Perfume Example VI Cocoanut oil (saponification number approximately 250) 40-60 Water 40-50 Trisodium salt of ethylene diamine tetra-acetic acid 0.01-3.0 Potassium permanganate 0.001-2.0 Sodium lauryl sulfate 0-2.0 Coloring Oil of clove Example VII Cocoanut oil (saponification number approximately 250) 50.0 Water (distilled) 45.0 Tetrasodium salt of ethylene diamine tetraacetic acid 2.0 Potassium permanganate 2.0 Methyl parahydroxy benzoate 0-0.1

Example VlIl Cocoanut oil 49-99 Water 0-50 Alkali metal salt of diethylene triamine tetraacetic acid 0.01-3.0

Potassium permanganate 0.00l-3.0 Nonyl phenol polyethylene glycol ether 2.0

In preparing the cleaner, an aqueous solution of the sodium salts of the amino-acid is mixed thoroughly with agitation with the oil at room temperatures until the mixture is clear. Subsequently, an aqueous solution of the permanganate is added with agitation, which is solubilized in the oil. Initially, as more water is added in small increments, the oil begins to thicken and take on a gel appearance, but with further additions of the Water, the oil becomes more fluid until up to about 40-50 percent by weight of the mixture is water. At this point, the mixture becomes viscous and after still further additions until approximately 65 percent of the composition is water, with further agitation, the water is solubilized in the oil. The composition is completely transparent and is stable indefinitely without any separation or settling of the water.

The sequestering or solubilizing agent not only solubilizes the metal permanganate but also acts as a synergist for the permanganate to increase its germ killing efficiency. Any of the alkali metal salts of an alkylene polyamine polyacetic acid may be used satisfactorily, such as the sodium and potassium salts of ethylene diamine tetraacetic acid, propylene 1,2-diamine tetra-acetic acid, propylene 1,3-diarnine tetra-acetic acid, 1,4-butylene diamine tetra-acetic acid, and dipropylene 1,2-triamine pentaacetic acid.

These acids and the alkali metal salts thereof can be characterized by the formula wherein M is hydrogen or an alkali metal, R is an alkylene radical and x is zero or a positive integer.

The concentration of these alkylene polyamine acid salts will vary from 0.015.0 percent by weight of the total composition, the specific amount depending upon the relative proportions of the potassium permanganate and the type of base used in preparing the skin cleaner. Thus, for example, lesser amounts of the amino acid salts will be necessary in instances where small amounts of detergent or soap are used, since the latter also are effective as dispersants. Likewise, the amount of water, with or without detergents, will affect the amounts of dispersant to be used.

A modified composition is possible by using common potash or amine soaps in combination with the cleaner to insure good foaming properties. Soaps, such as the cocoanut oils soaps, are desirable for this purpose, or a modified version of the cocoanut oil soaps with small amounts of oleic or resorcinol acid soaps can be prepared by using mixtures of olive oil and cocoanut oil. Other foaming materials include the synthetic detergents, such as the sulfated fatty oils, fatty acid esters, sulfated higher fatty alcohols, sulfo-succinic esters, sulfonated polyoxyalkylene ethers of alkyl-phenols, and the fatty alkyl sulfoacetates.

The effectiveness of the permanganate-containing oleaginous skin cleaner in inhibiting colonies of Staphylococcus aureus is illustrated in that a small drop of the disinfectant cleaner was deposited on the surface of an inoculated medium. The inoculated medium was obtained by using a blood-agar plate which was inoculated with a culture of Staphylococcus aureus obtained from a boil. After i 24 hours, the inoculated medium was examined and found to have a zone of inhibited growth of the bacteria around the product of 2 mm. in thickness, thus indicating that this particular strain of bacteria is sensitive to or inhibited by the skin cleaner.

Other ingredients which can be used to modify the composition include the perfumed oils, such as oil of clove, cinnamon, and eucalyptus, and some of these perfumed oils, in addition to modifying the odor of the skin cleaner, have a degree of germicidal characteristics which add to the overall effectiveness of the composition.

For purposes of description, certain specific examples have been employed but these are meant to be illustrative only. Numerous variations may be made with respect to the particular materials employed, the amounts utilized, etc., without departing from the spirit of the invention. It is desired, therefore, to be limited only by the scope of the appended claims.

The invention claimed is:

1. An antiseptic skin-cleaning composition consisting essentially of 30 to 99% by weight of a vegetable oil, 0 to 65% by weight of water, 0.001 to 3.0% by weight of an alkali metal permanganate selected from the group consisting of sodium permanganate, potassium permanganate and mixtures thereof, 0 to 2.0% by weight of a synthetic organic detergent selected from the group consisting of anionic and nonionic detergents, and 0.01 to 5.0% by Weight of a polyamino-polycarboxylic acid sequestering agent selected from the group consisting of the alkali metal salts of diethylene-triamine penta-acetic acid, ethylenediamine tetra-acetic acid, propylene 1,2-diamine tetra-acetic acid, propylene 1,3-diamine tetra-acetic acid, 1,4- butylene diamine tetra-acetic acid, and dipropylene 1,2- triamine penta-acetic acid.

2. The composition of claim 1 further characterized in that the water is present in an amount ranging from about 10 to 50% by weight.

3. The composition of claim 1 further characterized in that the vegetable oil is selected from the group consisting of olive oil, castor oil, cottonseed oil, cocoanut oil and palm oil.

4. The composition of claim 1 further characterized in that the alkali metal salts of the polyamino-polycarboxylic acids are selected from the group consisting of sodium and potassium salts of diethylene-triamine penta-acetic acid, ethylenediamine tetra-acetic acid, propylene 1,2-diamine tetra-acetic acid, propylene 1,3-diamine tetra-acetic acid, 1,4-butylene diamine tetra-acetic acid, and dipropylene 1,2-triamine penta-acetic acid.

5. The composition of claim 4 further characterized in that the alkali metal salt of the polyamino-polycarboxylic acid is a sodium salt.

References Cited by the Examiner UNITED STATES PATENTS 1,809,082 6/1931 Urkov et al. 167-85 2,309,722 2/ 1943 Wilkes et al. 16791 2,333,093 11/1943 Dearborn 16791 2,856,298 10/ 1958 Watson. 2,904,468 9/ 1959 Davis et al. 167-58 3,072,529 1/ 1963 Sanders et al.

FOREIGN PATENTS 16,518 1889 Great Britain. 17,742 1889 Great Britain.

OTHER REFERENCES Condensed Chem. Dictionary, Reinhold Publ. Corp. (1961), p. 933.

Sequestrene, Geigy Ind. Chem. (1952), pp. 25, 27, 36, and 48 relied on.

ALBERT T. MEYERS, Primary Examiner.

JULIUS GREENWALD, Examiner.

W. SCHULZ, Assistant Examiner. 

1. AN ANTISEPTIC SKIN-CLEANING COMPOSITION CONSISTING ESSENTIALLY OF 30 TO 99% BY WEIGHT OF A VEGETABLE OIL, 0 TO 65% BY WEIGHT OF WATER, 0.001 TO 3.0% BY WEIGHT OF AN ALKALI METAL PERMANGANATE SELCTED FROM THE GROUP CONSISTING OF SODIUM PERMANGANATE, POTASSIUM PERMANGANATE AND MIXTURE THEREOF, 0 TO 2.0% BY WEIGHT OF A SYNTHETIC ORGANIC DETERGENT SELECTED FROM THE GROUP CONSISTING OF ANIONIC AND NONIONIC DETERGENTS, AND 0.01 TO 5.0% BY WEIGHT OF A POLYAMINO-POLYCARBOXYLIC ACID SEQUESTERING AGENT SELECTED FROM THE GROUP CONSISTING OF THE ALKALI METALS SALTS OF DIETHYLENE-TRIAMINE PENTA-ACETIC ACID, ETHYLENEDIAMINE TETRA-ACETIC ACID, PROPYLENE 1,2-DIAMINE TETRA-ACETIC ACID, PROPYLENE 1,3-DIAMINE TETRA-ACETIC ACID, 1,4BUTYLENE DIAMINE TETRA-ACETIC ACID, AND DIPROPYLENE 1,2TRIAMINE PENTA-AECTIC ACID. 